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Silicon pack cementation has been applied to improve the oxidation resistance of Zr2Al3C4. The Si pack coating is mainly composed of an inner layer of ZrSi2 and SiC and an outer layer of Al2O3 at 1200 °C. The growth kinetics of silicide coating at 1000–1200 °C obey a parabolic law with an activation energy of 110.3 ± 16.7 kJ/mol, which is controlled by inward diffusion of Si and outward diffusion of Al. Compared with Zr2Al3C4, the oxidation resistance of siliconized Zr2Al3C4 is greatly improved due to the formation of protective oxidation products, aluminosilicate glass, mullite, and ZrSiO4.
Recent experiments have revealed that the wax on the lotus leaf surface, by itself, is weakly hydrophilic, even though the lotus leaf is known to be superhydrophobic. Conventional understanding suggests that a surface of such waxy composition should not be able to support superhydrophobicity and high contact angles between a liquid and the surface. Here, we show that the unexpected superhydrophobicity is related to the presence of “reentrant texture” (that is, a multivalued surface topography) on the surface of the lotus leaf. We exploit this understanding to enable the development of superoleophobic surfaces (i.e., surfaces that repel extremely low-surface-tension liquids, such as various alkanes), where essentially no naturally oleophobic materials exist. We also develop general design parameters that enable the evaluation of the robustness of the composite interface on a particular surface. Based on these design parameters, we also rank various superhydrophobic and superoleophobic substrates discussed in the literature, with particular emphasis on surfaces developed from inherently hydrophilic or oleophilic materials.
A novel ZnO seedless chemical approach for density-controlled growth of ZnO nanowire (NW) arrays has been developed. The density of ZnO NWs is controlled by changing the precursor concentration. Effects of both growth temperature and growth time are also investigated. By this novel synthesis technique, ZnO NW arrays can grow on any substrate (polymer, glass, semiconductor, metal, and more) as long as the surface is smooth. This technique represents a new, low-cost, time-efficient, and scalable method for fabricating ZnO NW arrays for applications in field emission, vertical field effect transistor arrays, nanogenerators, and nanopiezotronics.
A novel vapor-transport-assisted wet chemistry process was developed to fabricate oxide nanodot arrays from soft polymer templates. The feasibility and wide applicability of the proposed process was demonstrated with creation of high-density oxide nanodot arrays of TiO2, ZnO, and Co3O4. The present process not only avoids the over-growth problem inevitable in wet chemistry processes but also enables formation of oxide nanodots at low temperatures. The process can be readily extended to other compound systems in which the products can be formed through reactions of two reactants, one in liquid phase and the other in vapor phase.
This work reports on thermal and electrical conductivities and interface resistances for transport along aligned multiwalled carbon nanotubes (CNT) films grown on a nickel superalloy (Inconel) substrate. The measured specific thermal resistance of the combined Inconel–CNT and indium–CNT interfaces is of the same order as reported for CNT and silicon or SiO2 interfaces but much higher than theoretical predictions considering perfect contact between the tubes and substrate. Imperfect mechanical contact with the substrate and a large contribution caused by indium–CNT interface are thought to be mainly responsible for the high interface resistances and the low effective values of thermal and electrical conductivities. However, reported results represent an incentive for further research on CNT synthesis on metallic substrates for thermal management applications and pave the way for much easier integration of carbon nanotubes in electronic applications.
Aluminum nitride was bonded with a titanium foil at 1400 °C for up to 1 h in Ar. The AlN/Ti interfacial reactions were investigated using analytical electron microscopy. Reaction layers, consisting of δ-TiN, τ2-Ti2AlN, γ-TiAl, α2-Ti3Al, a two-phase region (α2-Ti3Al + α-Ti), and α-Ti (Al, N) solid solution, were observed after annealing at 1400 °C for 0.1 h. Among these phases, the α2-Ti3Al and (α2-Ti3Al + α-Ti) were formed during cooling. Further diffusion of N atoms into the reaction zone precipitates a chopped fiber-like α2-Ti2AlN in the matrix of γ-TiAl, with [110]γ−TiAl//[11¯20]τ2−Ti2AlN and (1¯1¯1)γ−TiAl//(1¯10¯3)τ2−Ti2AlN, by substituting N atoms for one-half Al atoms after annealing at 1400 °C for 1 h. The released Al atoms, due to the precipitation of τ2-Ti2AlN, resulted in an ordered Al-rich γ-TiAl or Ti3Al5. Furthermore, the α-Ti (Al, N) was nitridized into a lamellar layer (δ-TiN + α-Ti) with [110]δ−TiN//[11¯20]α−Ti and (111)δ−TiN//(0001)α−Ti.
A fully dense nanocrystalline (nc) Cu with mean grain size of 72 nm and a broad grain size distribution was synthesized by electrodeposition. Uniaxial tensile tests were done at different strain rates and room temperature. A very high strength of 1.04 G was obtained at strain rate of 0.1 s−1. The nearly perfect plasticity with a large strain of close to 20% was displayed at specific low strain rates of 4 × 10−5 to 10−4 s−1. With increasing strain rate, the nearly perfect plasticity disappeared. Strain rate sensitivity and activation volume of the nc Cu were estimated from the flow stress at a fixed strain of 1% and a strain rate change (jump) test. It was deduced from the high strain rate sensitivity exponent of 0.08 and small activation volume of 12b3 that both dislocation and grain boundary activities would take place in this nc Cu, which explained the nearly perfect plasticity observed in the tensile test.
Self-healing polymers have experienced rapid technological advancement over the past seven years. They have moved from a conceptual demonstration to practical application in this time frame and have grown from a single design to a generic paradigm for modern materials development. Potential applications of self-healing polymers are quite broad, including microelectronic substrates and encapsulants, polymeric paints and coatings, structural composites, and biomedical devices. In this article, we focus on polymeric systems that heal in an autonomic fashion, that is, automatically and without human intervention. The types of systems under development and the future of this paradigm in advanced materials are discussed.
Anodized films of titanium were prepared under different controlled conditions in a water-based electrolyte containing fluorine ions, using either a constant potential or a potential gradually rising to 20 V. The films were then examined using transmission electron microscopy at different stages of growth, in particular, the very early stages of growth (30 s, 200 s, and 10 min) and when the ordered nano-tubular structure was finally established (2–4 h). The use of ramped voltage during the early stages of anodization allowed a well-interconnected porous network to develop and maintained active oxidation throughout anodization. The film, as formed, consisted mainly of amorphous oxide/hydroxides of titanium with small regions of nano-sized crystals. These were found more often in the denser regions of the amorphous network, particularly the arms of the coral-like structure that formed. As the anodized film grew in thickness, the pores tended to become aligned, leading to a surface layer of nanotubes on the electrode material. Electron optical characterization revealed that the nanotubes consist of a stack of rings where the passage of the current had been optimized.
In this paper, we systematically demonstrate the corrosion behavior and surface characteristics of a newly developed Cu36Zr48Ag8Al8 bulk metallic glass (BMG). The Cu36Zr48Ag8Al8 BMG exhibits excellent corrosion resistance in acidic and alkaline solutions without Cl− ions. The alloy is spontaneously passivated with a markedly low current density in 1 N H2SO4 solution. The formation of the bilayered passive film of the present alloy immersed in 1 N H2SO4 solution, which is composed mostly of Zr4+ cations in the exterior part and Zr4+- and Al3+-enriched cations in the inner part, could be responsible for the high corrosion resistance.
ZrO2 films deposited on silicon (100) substrates using pulsed-pressure metalorganic chemical vapor deposition (PP-MOCVD) with zirconium n-propoxide (ZnP) Zr(OC3H7)4 were dense and fully crystalline for substrate temperatures of 500 to 700 °C. Film thicknesses were 40 to 815 nm thick, measured after growth using ellipsometry and scanning electron microscopy (SEM). The growth rate was between 0.1 μm/h at 500 °C and 1 μm/h at 700 °C. Transmission electron microscopy (TEM) and x-ray diffraction (XRD) indicated an average grain size of 10 to 20 nm. There was a random orientation of cubic/tetragonal zirconia at the highest experimental temperature of 700 °C. SEM and atomic force microscopy (AFM) was used to characterize island height of discontinuous films in the initial stages of growth where defects in the substrate caused preferred nucleation of isolated particles. At later stages of growth, the average surface roughness of continuous films was 30 nm, which revealed a more uniform growth had developed. A growth model is proposed, and optimal growth conditions are suggested for targeted microstructures of ZrO2 films.
With thin solid film usage expanding in numerous technologies, reliable measurements of material properties such as yield strength become important. However, for thin solid films the measurement of yield strength is not readily available, and an alternative method to obtain this property is to measure hardness and convert it to yield strength. Tabor suggested dividing hardness by ∼3 to obtain yield strength, which has been used extensively, despite its shortcomings. Since the pioneering work of Tabor, researchers have performed numerical and experimental studies to investigate the relationships between hardness, yield strength, and elastic modulus, using the indentation technique. In this study, finite element analysis was performed to simulate the nanoscratch technique. Specifically, the nanoscratch finite element analysis was used to validate a previously developed analytical scratch hardness model. A full-factorial design-of-experiments was performed to determine the significant variables for the ratio of calculated scratch hardness to yield strength and a simple analytical prediction model for the ratio of hardness to yield strength was proposed.
CO-gas-sensing response of individual metal–oxide–metal (MOM) heterojunction nanowires (∼250 nm diameter) in the Au–NiO–Au system, where a nanoscale segment of NiO oxide (∼250 nm long) is sandwiched axially between Au nanowires, and between individual all-oxide NiO nanowires (∼250 nm diameter, ∼5 μm long), has been measured at 150 °C. While the all-oxide nanowires are highly resistive and show no measurable response, the MOM nanowires show ∼25% decrease in current with the introduction of 800 ppm CO. The response is reversible, but it is slow due to the low temperature used. MOM nanowires, by virtue of the nanoscale-dimension, low-resistance oxide segment and the high-quality “end-on” metal–oxide contact, are an attractive class of nanowire gas-sensing elements for potential use in multifunctional “bottom up” nanoelectronics.
Results on mechanical alloying of binary and ternary Mg–Ti-based mixtures are reported. Using fine-powdered reactants and a process-control-agent, a mixture of two face-centered cubic compounds is obtained. Using a coarse Mg precursor without addition of a milling agent results in a hexagonal-solid solution of Ti in Mg due to a lower oxygen content in the Mg starting material. Upon introduction of Ni or Al as a third element, the amount of dissolved Ti decreases to form a nanocrystalline secondary phase. The electrochemical charging capacity of the hexagonal compounds is far superior to that of the cubic ones, whereas the discharge capacity is significantly increased only upon addition of Ni. The secondary TiNi phase acts as a rapid diffusion path for hydrogen, greatly improving the rate capability of the alloys. The reversible hydrogen storage capacity reaches values of up to 3.2 wt% at room temperature for (Mg0.75Ti0.25)0.90Ni0.10.
Phases that are in equilibrium with BaR2CuO6+x (R=lanthanides and Y), such as the “green-phase” and “brown-phase” structural variants of BaR2CuO5 in bulk samples, are attractive choices for flux-pinning for coated conductor applications because of the guaranteed chemical stability. In films, high-temperature x-ray diffraction studies of Ba2RCu3O6+x superconductor deposited on SrTiO3 substrate using the trifluoroacetate solution method demonstrate that while BaNd2CuO5 (“brown-phase” structure) develops at 735 °C and 100 Pa pO2, neither BaGd2CuO5 nor Ba(Nd1/3Eu1/3Gd1/3)2CuO5 (both green-phase structure) form at these conditions. As a result, Ba2(Nd1/3Eu1/3Gd1/3)Cu3O6+x in thin films is in equilibrium with the brown-phase, and Ba2GdCu3O6+x is in equilibrium with Gd2O3 in the Ba–Gd–Cu–O system, in contrast to the bulk systems. Different phase relationships in the vicinity of the Ba2RCu3O6+x phase imply different phases are available for flux-pinning applications. These differences will need to be considered carefully in designing optimized superconducting coated conductors.
Electrical conductivities of various mullite/zirconia composites, as well as monolithic mullite and zirconia, were measured using AC impedance spectroscopy from 100 Hz to 10 MHz at temperatures ranging from 150 to 1300 °C. The impedance spectra of monolithic zirconia and mullite/zirconia composites showed two semicircles because of the contributions from grains and grain boundaries, while those of monolithic mullite had one semicircle due to the predominant contribution from grains. This indicates that the conductivities of the mullite/zirconia composites increased with zirconia content. The activation energies of electrical conduction in mullite and zirconia were about 65 and 79 kJ/mol, respectively, and those of mullite/zirconia composites were between 65 and 79 kJ/mol. While the conductivities of various composites at 1 MHz were fitted by Lichtenecker’s rule, the general mixing equation could be applied to the conductivities measured at 1 kHz.
Nanostructured carbon materials, including carbon nanotubes, nanofibers, and nanowalls, exhibit a wide range of interesting properties dictated by the many different bonding configurations. Many of these materials can possess superhydrophobic behavior when water drops are placed on their surfaces: these drops have high contact angles and can roll freely on the surfaces, which is desirable for self-cleaning. In this work, we prepared porous carbon films using a microwave plasma enhanced chemical vapor deposition technique. These films showed superhydrophobicity with contact angle of 150°, which was explained by the synergetic effect of the highly rough surface combined with the hydrogen terminated edges of graphene sheets. However, the condensed water drops can behave differently: the drops did not roll readily. This behavior mimicked that of water on lotus leaves and further demonstrated that the reported superhydrophobic behavior is a function of how the water gets on to the surfaces.
A number of physiological systems involve contact or indentation of solids with tensed surface layers. In this paper the contact problem of spherical indentation of a linear elastic solid, covered with a tensed membrane is addressed. Semianalytical solutions are obtained relating indentation force to contact radius, as well as contact radius to depth. Good agreement is found between derived equations and results from finite element method (FEM) simulations. In addition, effect of membrane on subsurface stresses is shown quantitatively and compared favorably to FEM results. This work is applicable to mechanical property assessment of a number of biological systems.